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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
  • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
  • B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
  • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/56—Platinum group metals
  • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals

Definitions

• the present invention relates to a catalyst for the selective oxidation of ethane to acetic acid and/or for the selective oxidation of ethylene to acetic acid, and to a process for the production of acetic acid utilising the aforesaid catalyst.
• Catalysts comprising molybdenum, vanadium and niobium in combination with oxygen for use in processes for the production of acetic acid by the oxidation of ethane and ethylene are known in the art from, for example, US 4,250,346, EP-A- 1043064, WO 99/20592 and DE 196 30 832.
• US Patent No. 4,250,346 discloses the oxidative dehydrogenation of ethane to ethylene in a gas phase reaction at relatively high levels of conversion, selectivity and productivity to ethylene at a temperature of less than about 550°C using as a catalyst a composition comprising the elements molybdenum, X and Y in the ratio Mo a X b Y c wherein X is Cr, Mn, Nb, Ta, Ti, V and/or W, and preferably Mn, Nb, V and/or W; Y is Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, and preferably Sb, Ce and/or U, a is 1, b is 0.05 to 1.0 and c is 0 to 2, and preferably 0.05 to 1.0, with the proviso that the total value of c for Co, Ni and/or Fe is less than 0.5.
• EP-A- 1043064 discloses a catalyst composition for the oxidation of ethane to ethylene and/or acetic acid and/or for the oxidation of ethylene to acetic acid which comprises in combination with oxygen the elements molybdenum, vanadium, niobium and gold in the absence of palladium according to the empirical formula : Mo a W b Au c N d Nb e Yf (I) wherein Y is one or more elements selected from the group consisting of : Cr, Mn, Ta, Ti, B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, U, Re, Te, La and Pd; a
• a catalyst that contains, in combination with oxygen, the elements molybdenum, vanadium, niobium and gold and one or more elements selected from the group consisting of boron, aluminium, gallium, indium, germanium, tin, lead, antimony, copper, platinum, silver, iron and rhenium, in the absence of palladium, to oxidise ethane and/or ethylene to acetic acid with a high selectivity to acetic acid. Furthermore, it has been found possible using the catalysts of the present invention, to achieve a high selectivity to acetic acid with reduced, for example, little, if any, selectivity to ethylene.
• Catalysts embraced within the formula (I) include :- Mo a W b Au c N d Nb e Sn f Mo a Au c N d Nb e Sn f
• Z is Sn, Ag, Fe or Re, especially Sn.
• Suitable catalysts having the formula (I) include:- Mo Looo No.423 ⁇ bo. ⁇ s Au 0 .oos Ago.oos O y ,
• catalyst compositions of the present invention are highly selective in converting ethane and/or ethylene to acetic acid.
• 50mol% preferably at least 60mol%, such as at least 70mol%, may be achieved.
• a high selectivity to acetic acid may be achieved in combination with a low, if any, selectivity to ethylene.
• the selectivity to ethylene is less than 25 mol%, preferably, less than 10 mol%, such as less than 5 mol%.
• the selectivity to acetic acid is at least 60mol%, such as at least 70mol% and the selectivity to ethylene is less than 15mol%, such as less than 10 mol%.
• selectivity refers to a percentage that reflects the amount of desired acetic acid product produced as compared to the total carbon in the products formed :-
• the catalyst compositions may be prepared by any of the methods conventionally employed for the preparation of catalysts.
• the catalyst may be prepared from a solution of soluble compounds and/or complexes and/or compounds of each of the metals.
• the solution is preferably an aqueous system having a pH in the range from 1 to 12, preferably from 2 to 8, at a temperature of from 20° to 100°C.
• a mixture of compounds containing the elements is prepared by dissolving sufficient quantities of soluble compounds and dispersing any insoluble compounds so as to provide a desired gram-atom ratio of the elements in the catalyst composition.
• the catalyst composition may then be prepared by removing the solvent from the mixture.
• the catalyst may be calcined by heating to a temperature of from 200 to 550°C, suitably in air or oxygen, for a period of from 1 minute to 24 hours. Preferably, the air or oxygen is slowly flowing.
• the catalyst may be used unsupported or supported.
• Suitable supports include silica, alumina, zirconia, titania, silicon carbide and mixtures of two or more thereof.
• the catalyst may be used in the form of a fixed or a fluidised bed.
• the present invention provides a process for the selective production of acetic acid from a gaseous mixture comprising ethane and/or ethylene which process comprises contacting the gaseous mixture with a molecular oxygen- containing gas at elevated temperature in the presence of a catalyst composition as hereinbefore described.
• Ethane is selectively oxidised to acetic acid and/or ethylene is selectively oxidised to acetic acid.
• ethane and optionally ethylene is oxidised to a mixture comprising acetic acid which may be used with or without the addition or removal of acetic acid for the production of vinyl acetate by reaction with a molecular oxygen-containing gas in an integrated process.
• the feed gas comprises ethane and/or ethylene, preferably ethane.
• Ethane and/or ethylene may be used in substantially pure form or admixed with one or more of nitrogen, methane, carbon dioxide and water in the form of steam, which may be present in major amounts, for example greater than 5 volume percent or one or more of hydrogen, carbon monoxide, C 3 /C 4 alkenes and alkenes, which may be present in minor amounts, for example less than 5 volume percent.
• the molecular oxygen-containing gas may be air or a gas richer or poorer in molecular oxygen than air, for example oxygen.
• a suitable gas may be, for example, oxygen diluted with a suitable diluent, for example nitrogen.
• the elevated temperature may suitably be in the range from 200 to 500°C, preferably from 200 to 400°C.
• the pressure may suitably be atmospheric or superatmospheric, for example in the range from 1 to 50 bar, preferably from 1 to 30 bar.
• the catalyst composition is preferably calcined before use in the process of the invention. Calcination may suitably be achieved by heating at a temperature suitably in the range from 250 to 500°C in the presence of an oxygen-containing gas, for example air.
• an oxygen-containing gas for example air.
• a solution 'A' was prepared by dissolving 22.935 g of ammonium molybdate and 0.0357 g of ammonium gold chloride in 100 ml of distilled water at 70°C with stirring.
• a solution 'B' was prepared by dissolving 6.434 g of ammonium vanadate in 150 ml of distilled water at 70°C with stirring.
• a solution 'C was prepared by dissolving 7.785 g of ammonium niobium oxalate in 100 ml of distilled water at 70°C with stirring.
• Each of the solutions A, B and C was left for 15 minutes to allow maximum solubilisation of the components.
• Solution C was then added to solution B rapidly with stirring at 70°C.
• the mixed solution B/C was stirred for 15 minutes at 70°C then added rapidly to solution A.
• the final mixed solution A/B/C was left to stir at 70°C for a further 15 minutes, after which the solution was heated to boiling to facilitate evaporation of the water.
• Full evaporation of the reactant mixture was achieved in 1.5 hours, resulting in a dry paste.
• the beaker with the dried paste was then transferred to an oven for further drying at 120°C for 2 hours.
• the catalyst precursor was ground to a fine powder and then sieved through a 0.2 mm mesh sieve.
• the resulting powdered catalyst cake was then calcined in static air in an oven at 400°C for 4 hours.
• the nominal formula of the oxide catalyst obtained was : Moj.ooo No.423 ⁇ bn. ⁇ i5 Auo.0008 Oy
• This catalyst is not a catalyst according to the invention because it contains no element from the group consisting of B, Al, Ga, In, Ge, Sn, Pb, Sb, Cu, Pt, Ag, Fe and Re.
• a catalyst B was prepared as for catalyst A except that 0.0190 g of tin (II) chloride was additionally added to solution A.
• the nominal formula of the oxide catalyst obtained was :
• a catalyst C was prepared as for catalyst A except that 0.3792 g of tin (II) chloride was added to solution A.
• the nominal formula of the oxide catalyst obtained was :
• a catalyst D was prepared as for catalyst A but with addition of 0.0299 g of antimony (III) acetate (FW 298.88) to solution A.
• the nominal formula of the oxide catalyst was thus :
• catalyst E was prepared as for catalyst A but with addition of 0.0200 g of copper (II) acetate (FW 199.65) to solution A.
• the nominal formula of the oxide catalyst was thus :
• a catalyst F was prepared as for catalyst A but with addition of 0.0027 g of platinum acetate (FW 352.66) to solution A.
• the nominal formula of the oxide catalyst was thus :
• a catalyst G was prepared as for catalyst A but with addition of 0.0174 g of silver (I) acetate (FW 166.92) to solution A.
• the nominal formula of the oxide catalyst was -thus :
• a catalyst H was prepared as for catalyst A but with addition of 0.8080 g of ferric (III) nitrate (FW 404.00) to solution A.
• the nominal formula of the oxide catalyst was thus :
• a catalyst I was prepared as for catalyst A but with addition of 0.0268 g of ammonium rhenate (FW 268.24) to solution A.
• the nominal formula of the oxide catalyst was thus :
• a catalyst J was prepared as for catalyst A but with addition of 0.0256 g of gallium nitrate (FW 255.74) to solution A.
• the nominal formula of the oxide catalyst was thus :
• a powdered catalyst A to J was mixed with 15 ml of glass beads of diameter 0.4 mm to form a diluted catalyst bed of 20 ml in volume.
• the diluted catalyst was then loaded into a fixed bed reactor made of Hastelloy of dimensions 12 mm internal diameter and length 40 cm.
• the catalyst was maintained in position in the centre of the reactor using quartz wall plugs with inert packing material above and below the catalyst bed.
• the apparatus was then pressure-tested at 20 bar with helium to check for -leaks.
• the catalyst was then activated by heating to 220°C at 5°C/min in helium at 16 bar for 1 hour, to ensure full decomposition of catalyst precursors.
• the setpoint temperature of the reactor was increased to 293°C, to achieve a similar reactor temperature of 299-301 °C for each of catalysts A-J, in order to facilitate direct comparison.
• liquid product collection was commenced and continued for a period of typically 18 hours.
• the effluent gas composition was measured using GC analysis (ProGC, Unicam). Exit gas volume was measured over the run period by a water-gas meter. The liquid products were collected and weighed after the run period.
• Composition of the liquid products was measured using gas chromatography analysis (Unicam 4400 and 4200 fitted with TCD and FID detectors respectively).
• Each catalyst A to J was employed in the general reaction method described above. The results are given in Tables 1. Each catalyst was evaluated under standard conditions indicated in Table 1.

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